This invention relates to mixed gas refrigerant (MR), and more particularly to mixed refrigerant for use as a replacement of an existing chlorofluorocarbon refrigerant.
Chlorinated fluorocarbon refrigerants (CFC) have been implicated in causing environmental damage. Specifically, these gases which are very inert, are released from the refrigeration systems at ground level and diffused into the upper atmosphere. Because of their inertness, the gases are able to survive without decomposition until they reach the stratosphere where they are broken down by ultraviolet radiation, releasing chlorine atoms which break down the stratospheric ozone layer. There has recently been considerable concern about reductions in stratospheric ozone levels and this has led to bans on certain CFC's such as R-12, R-11, and others.
In automobile air conditioning systems, typically R-12 has been utilized. As such has been banned for future use after a given phase-out period, alternatives have been considered. At present, the most widely used refrigerant for replacement of R-12 for automobile air conditioning use has been R-134A. While this material comprised of C.sub.2 H.sub.2 F.sub.4 is ozone safe, it will not work in most existing automobile air conditioning systems using R-12 without expensive retro-fitting. Various automobile manufacturers are already installing new equipment in new automobiles scheduled for future sales which will accommodate the R-134A refrigerant. However, for the many existing automobiles, the imposition of the restrictions on R-12 will require such retro-fitting Knowledgeable estimates predict a costly conversion requirement to convert the air conditioning systems to make it compatible with R-134A.
Considerable efforts are being made to provide a replacement for R-12 in order to permit utilization of existing automobile air conditioning systems without unnecessary expensive retro-fitting. One type of refrigerant that has been given considerable attention are the hydrocarbons and, especially, propane. While propane has many useful thermodynamic properties which could perhaps serve as a replacement for R-12, unfortunately, its flammability prohibits its direct use. Proposals have therefore been to combine various hydrocarbons with other ingredients in order to provide an adequate mixture for replacement of R-12.
Hydrocarbon mixtures in general provide excellent thermodynamic properties for replacement of R-12, as well as other refrigerants which are being banned. However, numerous very rigorous standard exist for flammability testing and in order to meet some of the most restrictive flammability standards, it is necessary to greatly restrict the hydrocarbon content even though it may sacrifice the thermodynamic properties.
Furthermore, in designing a specific mixture, additional factors and constraints must be taken into consideration. Specifically, there are environmental safety conditions which must be met including sufficiently low ozone depletion potential, as well as sufficiently low global warming potential. Furthermore, the ultimate result should be of low toxicity.
There also exist additional constraints which must be met including material compatibility so that the resulting refrigerant will not deteriorate the material from which the systems are constructed. As to developing a replacement refrigerant, one of the most important parameters is hose penetration. Oil compatibility is also a severe problem since the oil must be a part of the air conditioning system and the gas mixture must be able to accommodate oils that are already on the market, including certain synthetic akylbenzenes and esters.
The mixed refrigerant must also be compatible with the particular equipment that is being utilized within the refrigerating system. There also exist the performance requirement so that the mixture must have its thermodynamic characteristics closely match those of the refrigerant being replaced and must have a co-efficient of performance sufficiently high to provide efficient results with the system being utilized.
An additional problem is with respect to the relationship of the boiling point of the components in a mixed gas refrigerant. When taking a blend of components, in most cases as the temperature increases, the component with the highest boiling point escapes faster and the liquid phase tends to become enriched with the components of lower boiling point. If the remaining components are of greater flammability, then even if the original composition is not of a flammable nature, the liquid phase remaining becomes of a flammable nature. Furthermore, a problem also exists in the escaping vapor phase if that is passing an environment that might cause flammability. Thus, the differential escape rate of the various components must be addressed to avoid having a greater amount of flammable components after evaporation of other of the components.
The above problem is even further compounded in that the situation is not consistent with all components. It is well known, that where components join to provide azeotropic mixtures, the separation between the components does not proceed in the same sequence as does the respective sequence of their decreasing boiling points. On the contrary, for azeotropic mixtures it works in reverse. Thus, the escape is not necessarily in accordance with the sequence of the boiling points of the components in the overall mixture.
Finally, there are commercial aspects, namely the components of the mixture should be relatively cheap and available on the market.
In designing mixtures to meet some of these constraints, sacrifices must be made. For example, while hydrocarbons provide good oil compatibility, they are of high flammability. On the other hand, fluorocarbons are generally of flame-retardant capabilities, however, they present problems with oil compatibility. Each of these has its own unique ozone depletion potential and global warming potential, and generally, it is required that the ozone and global problem should not be worse than the levels which may be acceptable according to the current government regulations.
In connection with the automobile air conditioning business, the flammability tests imposed are so severe that the presence of hydrocarbon itself or any other flammable material must be severely limited.
It has therefore become of significance to try and provide a replacement for R-12 in order to avoid the necessity of redesigning and retrofitting existing air conditioner compressors in automobiles. Numerous recommendations have thus far been made with many, many blends being suggested. While some of these provide certain of the features required, thus far most if not all of them have failed on other tests. For example, while many of them provide initial non-flammability properties, during continued testing of the rigorous flammability tests required in the automobile industry these mixtures have failed. Others have failed because they are permeable to the hoses. Accordingly, while there have been many, many suggestions, but thus far there has been no clear replacement that has been acceptable.
Additionally, because of the numerous available components that can be utilized in various mixture combinations, and because of the various percentages of utilization of each of these components, the number of possibilities is almost infinite and the ability to be able to provide an optimized replacement which satisfies all of the conditions has been a most challenging problem.
In co-pending application Ser. No. 08/180,208, assigned to the assignee of the present invention, there has been disclosed a unique refrigerant composition which has been able to satisfy the aforementioned conditions. Specifically, the refrigerant composition described comprises the basic mixture of 61-65 molar percent of tetrafluoroethane R134a (C.sub.2 H.sub.2 F.sub.4); 28-32 molar percent of monochlorotetra fluoroethane R124 (C.sub.2 HCl.sub.4) and 4-9 molar percent n-butane. This mixture was found to provide optimum replacement characters for existing R12 refrigerant. In another embodiment the mixture comprises 53-57 molar percent of R134a; 35-39 molar percent of R124 and 6-10 molar percent of n-butane.